FR2848428A1 - COSMETIC COMPOSITION AND METHOD FOR THE TREATMENT OF KERATINIC MATERIALS, COMPRISING A PHOTODIMERISABLE COMPOUND - Google Patents

Abstract

The present invention relates generally to a cosmetic composition comprising at least one cosmetic active agent and at least one photodimerizable compound making it possible to produce a deposit of material on keratin materials, which is persistent on washing, the location of which is controlled from precisely, capable of providing lasting cosmetic properties to keratin materials, and removable at any time.

Description

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 The present invention relates in general to a cosmetic composition comprising at least one cosmetic active agent and at least one photodimerizable material allowing the production of a deposit of material on keratin materials, and in particular on the hair, which is persistent in washing , whose location is precisely controlled, capable of providing lasting cosmetic properties to keratin materials, and can be removed at any time.

 The resistance of a deposit of material to washing can be provided by a low solubility of the deposit in aqueous detergent media.

 The fact of causing crosslinking by the action of light (photocrosslinking) makes it possible to selectively crosslink a deposit, in particular on specific areas of keratinous materials previously coated with the photocrosslinkable composition, and thus to create a lasting deposit on certain areas and no d 'other. The non-irradiated parts of the deposit (for example covered with a mask), and therefore not crosslinked, remain soluble. They can then be easily removed during rinsing or shampooing after irradiation. It thus becomes possible, for example, to create patterns on keratin materials and images using various stencils and masks with a photocrosslinkable composition, for example colored, or even to treat only specific sensitized areas, such as the tips in the case of hair, with a conditioning composition or the like.

 It is known to those skilled in the art to use photocrosslinkable materials such as materials derived from vinyl monomers, and in particular (meth) acrylate monomers.

 Thus, US Patent 5,300,285 describes a process for waving the hair and a composition for implementing this process, and in particular a neutralizing composition based on silicone, comprising a silicone with vinyl function, a phonitoinitiator with free radicals and a solvent. This composition acts as a substitute for neutralizing solutions based on hydrogen peroxide when applied to the hair after a process of permanent deformation of the hair and photocrosslinking of the composition. This composition has the advantage of functioning simultaneously as a crosslinking agent for keratin, while conferring advantages on the hair such as conditioning and

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 soft touch. The photocrosslinking of the composition is triggered by the photoinitiator (generally a derivative of acetophenone), which releases a radical under irradiation in the area of CUVA (350-385 nm).

 Unfortunately, the photopolymerization of vinyl-functional silicone in the presence of a photoinitiator leads to an irreversible photocrosslinking of the vinyl-functional silicone. In other words, once photocrosslinked, the deposit cannot be easily and at any time removed from the hair.

 In addition, in addition to the toxicologically unfavorable aspects of these monomers and of the photoinitiator, the compositions containing these materials derived from vinyl monomers are known to be unstable, in particular because of their sensitivity to oxygen and to humidity. In addition, photocrosslinking is sometimes obtained with prolonged irradiation, hence the risks of hair degradation under the action of UV.

 Finally, Japanese patent JP 09249812 describes interpenetrating networks containing molecules forming chelates and their uses, and more particularly compositions containing polymers of polyvinyl acetate type partially saponified with stilbazolium groups, crosslinked and containing chelating agents. This previously crosslinked material can then be used as it is in medical or cosmetic applications. However, there is no mention in this patent (JP 09249812) of applying a composition containing non-crosslinked polymers to the hair or the skin before irradiation.

 The object of the present invention is therefore to provide a cosmetic composition which, after application to keratin materials, in particular to keratin fibers such as the hair, is photocrosslinked in a possibly reversible manner, and results in a crosslinked deposit which does not dissolve , is persistent in washing and does not degrade the keratinous fiber, thus guaranteeing the durability of the cosmetic effects provided by this deposit.

 By reversible photocrosslinking of a material or a composition is meant, within the meaning of the present application, a crosslinking by action of the light of the material or of the composition, resulting in a deposit which can be removed at any time and easily hair. Thus, irradiation in the UVB domain (around 250 nm) leads to the reformation of the original double bonds and to the disappearance of the crosslinking.

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 In particular, the subject of the present invention is a cosmetic composition for the treatment of keratin materials comprising at least one cosmetic active agent, characterized in that it additionally comprises at least one compound comprising at least one photodimerizable group.

 By cosmetic active is meant, within the meaning of the present invention, any active compound having cosmetic or dermatological activity.

 By photodimerizable group is meant, within the meaning of the present invention, a chemical group leading to photodimerization reactions under irradiation.

 By photodimerization is meant, within the meaning of the present invention, a chemical reaction between two double bonds (of type 2 + 2) or two pairs of double bonds (of type 4 + 4).

The case of a reaction between two double bonds can be schematized as follows:

These photodimerization reactions are defined in the document Advanced Organic Chemistry, J Marck, 4th edition, Wiley Interscience, NY 1992, p 855.

 Materials having photodimerizable groups according to the invention have the advantage of being stable with respect to oxygen, humidity, and heat, and leading to reversible crosslinking.

 In addition, the photodimerizable groups according to the invention are very photosensitive. Consequently, even low energy irradiation leads to rapid and effective crosslinking of the material, which, in the case of a cosmetic application, induces a short duration and low energy irradiation which does not lead to degradation of the keratin materials.

 Preferably, the photodimerizable groups which can be used according to the invention are chosen from monovalent radicals of formulas:

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dans lesquelles : - Y et Z désignent indépendamment l'un de l'autre un atome de carbone ou d'azote, - A est un groupe de liaison divalent choisi parmi les radicaux alkylènes, les radicaux cycloaromatiques, les radicaux hétérocycliques, les radicaux carbonyles, les radicaux alcénylènes et leurs combinaisons, - B est un groupe monovalent choisi parmi les radicaux alkyles, les radicaux cycloaromatiques, les radicaux hétérocycliques, les radicaux carbonyles, les radicaux alcényles et leurs combinaisons, - X est un groupe divalent choisi parmi les radicaux alkylènes, les radicaux cycloaromatiques, les radicaux hétérocycliques, les radicaux carbonyles, les radicaux alcénylènes et leurs combinaisons, et chacun des groupes cités pouvant éventuellement être substitué par un ou plusieurs groupements choisi (s) parmiles groupements alkyles, hydroxy, amino, mono ou dialkylamino, halogènes, aryles, carboxy, alcoxy, alcoxycarbonyles, hydrogénocarbonyles, sulfonato, amide, et acyles.

in which: - Y and Z denote independently of one another a carbon or nitrogen atom, - A is a divalent linking group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals , alkenylene radicals and their combinations, - B is a monovalent group chosen from alkyl radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenyl radicals and their combinations, - X is a divalent group chosen from alkylene radicals , cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and their combinations, and each of the groups mentioned possibly being substituted by one or more groups chosen from alkyl, hydroxy, amino, mono or dialkylamino groups, halogens, aryls, carboxy, alkoxy, alkoxycarbonyls, hydrogen carbonyls, sulfonato, amide, and acy the.

 The dimerizable groups according to the invention are in particular those cited in patents US-2,811,510, EP 0 313 220, EP 0 313 221, EP 092 901, GB 2 030 575 and GB 2 076 826, as well as in the articles Chemical review Vol 83.5 1983, p 507 Polym, Paint color Journal 1988, 178, p 209 and Current Trends in Polymer Photochemistry, Ellis Morwood edition, NY, 1995.

 By way of example, mention may be made more particularly of the photodimerizable groups chosen from monovalent radicals of the following compounds:

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où - R représente l'atome d'hydrogène, un groupement alkyle ou hydroxyalkyle, et - R' représente l'atome d'hydrogène ou un groupement alkyle, - styrylazolium de formule :

où A désigne un atome de soufre, un atome d'oxygène, ou un groupement NR' ou C(R')z, R et R' étant tels que définis précédemment, - styrylpyrazine, - chalcone, - (thio)cinnamate et (thio)cinnamamide, - maléimide, - (thio)coumarine, - thymine, - uracile, - butadiène - anthracène, - pyridone, - pyrrolizinone, - sels d'acridizinium, - furanone, - phénylbenzoxazole, et - leurs dérivés. - stilbene, - styrylpyridinium (stilbazolium) of formula:

where - R represents the hydrogen atom, an alkyl or hydroxyalkyl group, and - R 'represents the hydrogen atom or an alkyl group, - styrylazolium of formula:

where A denotes a sulfur atom, an oxygen atom, or a group NR 'or C (R') z, R and R 'being as defined above, - styrylpyrazine, - chalcone, - (thio) cinnamate and ( thio) cinnamamide, - maleimide, - (thio) coumarin, - thymine, - uracil, - butadiene - anthracene, - pyridone, - pyrrolizinone, - acridizinium salts, - furanone, - phenylbenzoxazole, and - their derivatives.

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 Such chemical groups have activated double bonds, so that the photodimerization of these double bonds is triggered spontaneously in the UVA domain, without requiring a photoinitiator.

 By photoinitiator is meant, within the meaning of the present invention, a compound which initiates the photodimerization reaction and releases a radical under irradiation, in particular in the UV field.

 Consequently, when the composition according to the invention comprises a compound comprising at least one photodimerizable group chosen from the photodimerizable groups previously mentioned, it is preferably free of photoinitiator.

 The compounds with photodimerizable group (s) according to the invention are preferably not dyes.

 The photodimerizable groups according to the invention can be easily grafted onto any type of support compound.

 Preferably, the support compound is chosen from polymers, and even more preferably from poly (vinyl) polymers and polydiorganosiloxanes.

 Among the polyvinyl polymers, polyvinyl acetate, preferably partially saponified, are particularly preferred.

 The compound (s) comprising at least one photodimerizable group according to the invention can (or can) thus be a polymer soluble or dispersed in the composition, or a polymer adsorbed on polymer particles, themselves dispersed in the composition. In the latter case, the polymer particles are preferably particles of vinyl polymers, and better still particles of polyvinyl acetate.

 The compound (s) comprising at least one photodimerizable group according to the invention represents (s) preferably 0.01 to 25%, better 0.1 to 20%, and better still 1 to 15% of the total weight of the composition.

 The cosmetic composition according to the invention may, in addition, comprise an effective amount of at least one photosensitizer.

 By photosensitizer is meant within the meaning of the present invention, an ingredient which modifies the wavelength of the irradiation, thus triggering the photodimerization reaction.

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 For example, the photodimerization of dimethylmaleimide groups is triggered by irradiation centered on the wavelength range from 270 to 300 nm. In the presence of a photosensitizer such as thioxanthone, photodimerization becomes effective with irradiation centered on the wavelength range from 360 to 430 nm.

 Among the photosensitizers which can be used according to the invention, there may be mentioned in particular thioxanthone, bengal rose, phloxin, eosin, erythrosin, fluorescein, acriflavin, thionin, riboflavin, proflavin, chlorophylls , hematoporphyrin, methylene blue and mixtures thereof.

 In practice, the photosensitizer which can be used according to the invention represents 0.00001% to 5% by total weight of the composition.

 The cosmetic active ingredient (s) according to the invention is (are) chosen from: * saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, * amino acids, oligopeptides, peptides, hydrolyzed proteins or not, modified or not, polyamino acids, enzymes, * branched and unbranched fatty acids and alcohols, * animal, vegetable or mineral waxes, * ceramides and pseudo-ceramides, * hydroxylated organic acids, * UV filters, * antioxidants and anti-free radical agents, * chelating agents, * dandruff agents, * seborrhea regulating agents, * soothing agents, * cationic surfactants, * cationic, amphoteric polymers, * organomodified or unorganized silicones, * mineral, vegetable or animal oils, * polyisobutenes and poly (a-olefins), * esters,

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 * soluble or dispersed anionic polymers, * soluble or dispersed nonionic polymers, * reducing agents, * coloring matters, and in particular hair dyes, * foaming agents, * film-forming agents, * particles, and their mixtures.

 In general, the saccharide, oligosaccharide or polysaccharide type compounds, hydrolyzed or not, modified or not, which can be used in the present invention, are chosen from those which are in particular described in "Encyclopedia of Chemical Technology, KirkOthmer, Third Edition, 1982 , volume 3, pp. 896-900, and volume 15, pp 439-458 ", in" Polymers in Nature, by EA MacGREGOR and CT

GREENWOOD, Editions John Wiley & Sons, Chapter 6, pp 240-328,1980 "and in Industrial Gums - Polysaccharides and their Derivatives, Edited by Roy L. WHISTLER, Second Edition, Edition Academic Press Inc.", the contents of these three works being fully included in this application for reference.

 By way of examples of saccharides, oligosaccharides, polysaccharides hydrolyzed or not, modified or not, which can be used in the invention, mention may be made in particular of glucans, starches modified or not (such as those obtained, for example, from cereals such as wheat, corn or rice, vegetables like light peas, tubers like potatoes or cassava) and different from starch betainate as described above, amylose, amylopectin, glycogen dextrans, ss-glucans, celluloses and their derivatives (methylcelluloses, hydroxyalkylcelluloses, ethylhydroxyethylcelluloses, carboxymethylcelluloses), fructosans, inulin, levane, mannans, xylans, lignins, arabans, galactans, galacturonans, chitin, glucoronoxylans, arabinoxylans, xyloglucans, galactomannans, glucomannans, pectic acids and pectins, alginic acid and alginates, arabinogalactans, carragh enins, agars, glycosaminoglucans, gum arabics, Tragacanth gums, Ghatti gums,

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 Karaya gums, carob gums, guar gums and xanthan gums.

 As amino acids, there may be mentioned, for example, cysteine, lysine, alanine, N-phenylalanine, arginine, glycine, leucine, and mixtures thereof. As oligopeptides, peptides, proteins hydrolyzed or not, modified or not, which can be used according to the invention, mention may in particular be made of hydrolysates of wool or silk proteins, modified or not, proteins vegetables such as wheat proteins.

 Among the amino acids which can be used, mention may be made of polylysine.

 Among the enzymes which can be used, mention may be made of laccases, peroxidases, lipases, proteases, glycosidases, dextranases, uricases, alkaline phosphatase.

 Among the branched fatty acids or not suitable for the present invention, mention may in particular be made of C8-C30 carboxylic acids, such as palmitic acid, oleic acid, linoleic acid, myristic acid, acid stearic, lauric acid, and mixtures thereof. The fatty alcohols which can be used in the present invention include in particular the C8-C30 alcohols such as, for example, palmityl, oleyl, linoleyl, myristylic, stearyl and lauryl alcohols.

 A wax, within the meaning of the present invention, is a lipophilic compound, solid at room temperature (approximately 25 ° C.), with reversible solid / liquid state change, having a melting temperature above approximately 40 ° C. and capable of going up to at 200 C, and exhibiting an anisotropic crystal organization in the solid state. In general, the size of the crystals of the wax is such that the crystals diffract and / or scatter light, giving the composition which comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized from the oils of the mixture, microscopically and macroscopically detectable (opalescence).

 As waxes which can be used in the present invention, mention may be made of waxes of animal origin such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as

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 Carnauba, Candellila, Ouricury, Japan, cocoa butter or cork fiber or sugar cane waxes; mineral waxes, for example, paraffin, petrolatum, lignite or microcrystalline waxes or ozokerites.

 Among the ceramides, mention may be made in particular of the ceramides of classes I, II, III and V according to the classification of DAWNING, and more particularly N-oleyldehydrosphingosine.

 The hydroxylated organic acids are chosen from those well known and used in the art. Mention may in particular be made of citric acid, lactic acid, tartaric acid, malic acid.

 The active UV-A and / or UV-B sun filters that can be used according to the invention are those well known to those skilled in the art. Mention may in particular be made of dibenzoylmethane derivatives such as 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4dimethyldibenzoylmethane, 4-tert-butyl-4'-diisopropyldibenzoyl -amino-benzoic and its esters such as 2-ethylhexyl p-dimethylaminobenzoate and N-propoxylated ethyl p-aminobenzoate, salicylates such as triethanolamine salicylate, cinnamic acid esters such as 4-methoxy - 2-ethylhexyl cinnamate, methyl diisopropylcinnamate, menthyl anthranilate, benzotriazole derivatives, triazine derivatives, ss, ss'-diphenylacrylate derivatives such as 2-cyano-3,3diphenylacrylate ethylhexyl and ethyl 2-cyano-3,3-diphenylacrylate, 2-phenylbenzimidazole-5-sulfonic acid and its salts, benzophenone derivatives, benzylidene-camphor derivatives, silicone filters, etc.

 As antioxidants and anti-free radical agents which can be used in the present invention, there may be mentioned, for example, ascorbic acid, ascorbylated compounds such as ascorbyl dipalmitate, tbutylhydroquinone, polyphenols such as phloroglucinol, sodium sulfite, erythorbic acid, flavonoids.

 The chelating agents can be chosen in particular from EDTA (ethylenediaminetetraacetic acid) and its salts such as disodium EDTA and dipotassium EDTA, phosphate compounds such as sodium metaphosphate, sodium hexametaphosphate, tetrapotassium pyrophosphate, phosphonic acids and their salts such as the salts of ethylenediaminetetramethylenephosphonic acid.

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 The anti-dandruff agents are chosen, for example, from: - benzethonium chloride, benzalkonium chloride, chlorhexidine, chloramine T, chloramine B, 1,3-dibromo-5,5dimethylhydantoin, 1,3-dichloro 5,5-dimethylhydantoin, 3-bromo 1chloro 5,5-dimethylhydantoin, N-chlorosuccinimide; - 1-hydroxy-2-pyridone derivatives such as, for example, 1hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone and 1hydroxy-4,6-dimethyl- 2-pyridone; - trihalogenocarbamides; - triclosan; - azole compounds such as climbazole, ketoconazole, clotrinazole, econazole, isoconazole and miconazole b; - antifungal polymers such as amphotericin B or nystatin; - selenium sulfides - sulfur in its different forms, cadmium sulfide, allantoin, coal or wood tars and their derivatives in particular, cade oil, undecylenic acid, fumaric acid , allylamines such as terbinafine.

 They can also be used in the form of their physiologically acceptable acid addition salts, in particular in the form of salts of sulfuric, nitric, thiocyanic, hydrochloric, hydrobromic, hydroiodic, phosphoric, acetic, benzoic, glycolic, aceturic or succinic acids. , nicotinic, tartaric, maleic, palmitic, methanesulfonic, propanoic, 2-oxopropanoic, propanedioic, 2-hydroxy-1,4butanedioic, 3-phenyl-2-propenoic, a-hydroxybenzene acetic, ethanesulfonic, 2-hydroxyethane-sulfonic, 4- methylbenzenesulfonic, 4-amino-2-hydroxybenzoic, 2-phenoxybenzoic, 2-acetyloxybenzoic, picric, lactic, citric, malic, oxalic and amino acids.

 The anti-dandruff agents mentioned above can also optionally be used in the form of their physiologically acceptable organic or inorganic base addition salts. Examples of organic bases are in particular low molecular weight alkanolamines such as ethanolamine, diethanolamine, N-ethylethanolamine, triethanolamine, diethylaminoethanol, 2-amino-2-methylpropanedione;

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 non-volatile bases such as ethylenediamine, hexamethylenediamine, cyclohexylamine, benzylamine, N-methylpiperazine; quaternary ammonium hydroxides, for example, trimethylbenzyl hydroxide; guanidine and its derivatives, and in particular its alkylated derivatives. Examples of inorganic bases are in particular the salts of alkali metals, such as sodium or potassium; ammonium salts, alkaline earth metal salts, such as magnesium, calcium; the cationic di, tri or tetravalent metal salts, such as zinc, aluminum and zirconium.

Alkanolamines, ethylenediamine and inorganic bases such as the alkali metal salts are preferred.

 Seborrhea regulating agents are, for example, succinylchitosan and poly-p-alanine.

 Soothing agents are, for example, azulene and glycyrrhetinic acid.

 The cationic surfactants are those well known per se, such as the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyl-trialkylammonium, trialkylbenzylammonium, trialkylhydroxy-alkylammonium or alkylpyridinium; imidazoline derivatives.

 By "cationic polymer" is meant any polymer containing cationic groups and / or groups which can be ionized into cationic groups.

 The cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of hair treated with detergent compositions, namely in particular those described in patent application EP-A-0 337 354 and in French patent applications FR-A- 2 270 846, 2 383 660.2 598 611, 2 470 596 and 2 519 863.

 The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain, or be carried by a lateral substituent directly linked thereto.

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 The cationic polymers used generally have a number average molecular mass of between 500 and 5,106 approximately, and preferably between 103 and 3,106 approximately.

 Among the cationic polymers, mention may be made more particularly of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type. These are known products.

 The polymers of the polyamine, polyaminoamide, quaternary polyammonium type, which can be used in the composition of the present invention, are those described in French patents Nos. 2,505,348 and 2,542,997. Among these polymers, there may be mentioned: ( 1) homopolymers or copolymers derived from esters or amides of acrylic or methacrylic acid; (2) derivatives of cellulose ethers comprising quaternary ammonium groups described in French patent 1,492,597; (3) cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl or hydroxypropyl-celluloses grafted in particular with a salt of methacryloylethyl-tri methyla m mon iu m, of methacrylamidopropyltrimethylammonium or of dimethyldiallylammonium; (4) the cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups; (5) polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene groups with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers. Such polymers are described in particular in French patents 2,162,025 and 2,280,361; (6) water-soluble polyaminoamides, such as those described in particular in French patents 2 252 840 and 2 368 508; (7) polyaminoamide derivatives, for example, adipic acid / diakylaminohydroxyalkyldialkylene-triamine polymers in which the alkyl group contains from 1 to 4 carbon atoms and preferably denotes a

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 methyl group, ethyl, propyl, and the alkylene group contains from 1 to 4 carbon atoms, and preferably denotes the ethylene group. Such polymers are described in particular in French patent 1,583,363.

 (8) polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group, with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 atoms of carbon. The molar ratio between the polyalkylene-polylamine and the dicarboxylic acid being between 0.8: and 1.4:; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: and 1.8: Such polymers are described in particular in US patents 3,227 615 and 2,961,347; (9) alkyldiallylamine or dialkyldiallylammonium cyclopolymers such as the homopolymer of dimethyldiallyl ammonium chloride and copolymers of diallyldimethylammonium chloride and acrylamide; (10) quaternary diammonium polymers having a number-average molecular mass generally between 1000 and 100,000, such as those described, for example, in French patents 2,320,330, 2,270,846.2 316,271, 2,336,434 and 2,413,907 and US Patents 2,273,780.2 375,853.2 388,614.2 454,547.3,206,462,2,221,002,2,271,378.3,874,870,4001,432,3,929,990.3 966,904.4 005,193, 4,025,617, 4,025,627.4 025 653.4 026,945 and 4,027,020; (11) quaternary polyammonium polymers such as those described in particular in patent application EP-A-122 324; (12) quaternary polymers of vinylpyrrolidone and of vinylimidazole such as, for example, the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the company B.A.S.F. ; (13) polyamines such as Polyquart H sold by HENKEL, referenced under the name of "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary; (14) crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (Ci-C4) ammonium salts such as those sold under the name

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 SALCARE SC 92, SALCARE SC 95 and SALCARE # SC 96 by ALLIED COLLOIDS; and their mixtures.

 Other cationic polymers which can be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorohydrin, quaternary polyureylenes and chitin derivatives.

 The amphoteric polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C can denote groups deriving from zwitterionic monomers of carboxybétaines or sulphobetaines; B and C can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon group, or although B and C form part of a chain of a polymer with an ethylene-dicarboxylic unit, one of the carboxylic groups of which has been caused to react with a polyamine comprising one or more primary or secondary amine groups.

 The amphoteric polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers: (1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkyl-methacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of

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sodium acrylate / acrylamide propyltrimethylammonium chloride copolymer sold under the name Polyquart KE 3033 by the
HENKEL Company.

 The vinyl compound can also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride.

 The copolymers of acrylic acid and of the latter monomer are offered under the names MERQUAT # 280, MERQUAT # 295 and MERQUAT # PLUS 3330 by the company CALGON.

 (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen with an alkyl group, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

 The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are groups whose alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutylacrylamide, N-tertiooctylacrylamide, N- octyl. N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

 The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers are particularly used whose name CTFA (4th Ed, 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

 (3) crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of general formula:

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dans laquelle R10 représente un groupe divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atomes de carbone de ces acides ou d'un groupe dérivant de l'addition de l'un quelconque desdits acides avec une amine bis primaire ou bis dérivé secondaire, et Z désigne un groupe d'une polyalkylène-polyamine bis-primaire, mono ou bis-secondaire et représente de préférence : a) dans les proportions de 60 à 100 % en moles, le groupe

où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce groupe dérivant de la diéthylène-triamine, de la triéthylènetétraamine ou de la dipropylène-triamine; b) dans les proportions de 0 à 40 % en moles, le groupe (III) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylènediamine, ou le groupe dérivant de la pipérazine

c) dans les proportions de 0 à 20 % en moles, le groupe -NH-(CH2)6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement amine du polyaminoamide et alcoylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane-sultone ou de leurs sels.

in which R10 represents a divalent group derived from a saturated dicarboxylic acid, from an aliphatic mono or dicarboxylic acid having an ethylenic double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a group deriving from the addition of any one of said acids with a primary bis or secondary derivative bis amine, and Z denotes a group of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100% by moles, the group

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this group deriving from diethylene triamine, triethylenetetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (III) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the group deriving from piperazine

c) in the proportions of 0 to 20 mol%, the group -NH- (CH2) 6-NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides , dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane-sultone or their salts.

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 The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, 2,2,4-trimethyladipic and 2,4,4-trimethyladipic, terephthalic acids, ethylenically double-linked acids such as, for example , acrylic, methacrylic, itaconic acids. The alkane-sultones used in the alkylation are preferably propane- or butane-sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

dans laquelle R11 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent chacun un nombre entier de 1 à 3, R12 et R13 représentent un atome d'hydrogène, un groupement méthyle, éthyle ou propyle, R14 et R15 représentent un atome d'hydrogène ou un groupe alkyle de telle façon que la somme des atomes de carbone dans R14 et R15 ne dépasse pas 10. (4) polymers comprising zwitterionic units of formula:

in which R11 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z each represent an integer from 1 to 3, R12 and R13 represent a hydrogen atom, a methyl, ethyl group or propyl, R14 and R15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R14 and R15 does not exceed 10.

 The polymers comprising such units can also comprise units derived from non-zwitterionic monomers such as acrylate or methacrylate of dimethyl- or diethylaminoethyl, or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate .

 By way of example, there may be mentioned the copolymer of methyl methacrylate and of methyl dimethyl-carboxymethylammonio-ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

 (5) polymers derived from chitosan containing monomer units corresponding to the following formulas:

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le motif (V) étant présent dans des proportions comprises entre 0 et 30 %, le motif (VI) dans des proportions comprises entre 5 et 50 % et le motif (VII) dans des proportions comprises entre 30 et 90 %, étant entendu que dans ce motif F, R16 représente un groupe de formule:

dans laquelle si q=0, R17, R18 et R19, identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalkylamine ou un reste dialkylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alkylthio, sulfonique, un reste alkylthio dont le groupe alkyle porte un reste amino, l'un au moins des groupes R17, R18 et R19 étant dans ce cas un atome d'hydrogène ; ou si q=1, R17, R18 et R19 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.

the motif (V) being present in proportions of between 0 and 30%, the motif (VI) in proportions of between 5 and 50% and the motif (VII) in proportions of between 30 and 90%, it being understood that in this motif F, R16 represents a group of formula:

in which if q = 0, R17, R18 and R19, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more atoms of nitrogen and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the groups R17, R18 and R19 being in this case a hydrogen atom; or if q = 1, R17, R18 and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

 (6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl-chitosan or N-carboxybutyl-chitosan sold under the name EVALSAN by the company JAN DEKKER.

 (7) The polymers corresponding to the general formula (IX) described for example, in French patent 1,400,366:

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dans laquelle R20 représente un atome d'hydrogène, un groupe CH30, CH3CH20, phényle, R21 désigne l'hydrogène ou un groupe alkyle inférieur tel que méthyle, éthyle, R22 désigne l'hydrogène ou un groupe alkyle inférieur tel que méthyle, éthyle, R23 désigne un groupe alkyle inférieur tel que méthyle, éthyle ou un groupe répondant à la formule: -R24-N(R22)2, R24 représentant un groupement-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3)-, R22 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces groupes et contenant jusqu'à 6 atomes de carbone.

in which R20 represents a hydrogen atom, a CH30 group, CH3CH20, phenyl, R21 denotes hydrogen or a lower alkyl group such as methyl, ethyl, R22 denotes hydrogen or a lower alkyl group such as methyl, ethyl, R23 denotes a lower alkyl group such as methyl, ethyl or a group corresponding to the formula: -R24-N (R22) 2, R24 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3) -, R22 having the meanings mentioned above, as well as the higher homologs of these groups and containing up to 6 carbon atoms.

et X désigne le symbole E ou E', E ou E', identiques ou différents, désignent un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle, et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques ; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alcénylamine, des groupements hydroxyle, (8) Amphoteric polymers of the type -DXDX- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula: -DXDXD- (X) where D designates a group

and X denotes the symbol E or E ', E or E', which may be identical or different, denote a bivalent group which is a straight or branched chain alkylene group containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups, and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups,

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et X désigne le symbole E ou E' et au moins une fois E' ; ayant la signification indiquée ci-dessus et E' est un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs groupes hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude. benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane. b) The polymers of formula: -DXDX- (XI) where D denotes a group

and X denotes the symbol E or E 'and at least once E'; having the meaning given above and E 'is a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, whether or not substituted by one or more hydroxyl groups and comprising one or more several nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.

 (9) (C 1 -C 5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine These copolymers can also include other vinyl comonomers such as vinylcaprolactarne.

 The silicones which can be used in accordance with the invention may be soluble or insoluble in water, and they may in particular be polyorganosiloxanes insoluble in water; they can be in the form of oils, waxes, resins or gums.

 Organopolysiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968) Academic Press. They can be volatile or non-volatile.

 When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly still from:

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 (i) cyclic silicones containing from 3 to 7 silicon atoms and preferably 4 to 5. This is, for example, octamethylcyclotetra-siloxane marketed in particular under the name of "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2" by RHODIA, decamethylcyclopentasiloxane marketed under the name "VOLATILE SILICONE 7158" by UNION CARBIDE, "SILBIONE 70045 V 5" by RHODIA.

(ii) les silicones volatiles linéaires ayant 2 à 9 atomes de silicium et possédant une viscosité inférieure ou égale à 5.10-6m2/s à 25 C. Il s'agit, par exemple, du décaméthyltétrasiloxane commercialisé notamment sous la dénomination "SH 200" par la société TORAY SILICONE. Des silicones entrant dans cette classe sont également décrites dans l'article publié dans Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "SILICONE VOLATILE FZ 3109" sold by the company UNION CARBIDE, with a chemical structure:

(ii) linear volatile silicones having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10-6m2 / s at 25 C. This is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by TORAY SILICONE. Silicones included in this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics".

 Among the non-volatile silicones, mention may especially be made of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, gums and silicone resins, polyorganosiloxanes modified by organofunctional groups.

 The organomodified silicones which can be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon group.

 Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:

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 - polyethyleneoxy and / or polypropyleneoxy groups optionally comprising C6-C24 alkyl groups such as the products called dimethicone-copolyol marketed by DOW CORNING under the name DC 1248 or the oils SILWET L 722, L 7500, L 77, L 711 from the company UNION CARBIDE and the alkyl (C12) -methiconecopolyol marketed by the company DOW CORNING under the name Q2 5200; - substituted or unsubstituted amino groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company GENESEE or the products sold under the names Q2 8220 and DOW CORNING 929 or 939 by the company DOW CORNING. The substituted amino groups are in particular C1-C4 aminoalkyl groups; - thiol groups, such as the products marketed under the names "GP 72 A" and "GP 71" from GENESEE; - alkoxylated groups, such as the product sold under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX # 2428, 2434 and 2440 by the company GOLDSCHMIDT; - hydroxylated groups, such as the polyorganosiloxanes with a hydroxyalkyl function described in French patent application FR-A-85 16334, - acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in patent US-A-4957732.

 - Anionic groups of the carboxylic acid type such as, for example, in the products described in patent EP 186 507 of the company CHISSO CORPORATION, or of the alkyl-carboxylic type such as those present in the product X-22-3701 E of the company SHIN-ETSU; 2hydroxyalkylsulfonate; 2-hydroxyalkylthiosulfate such as the products sold by the company GOLDSCHMIDT under the names "ABIL S201" and "ABIL S255".

 - Hydroxyacylamino groups, such as the polyorganosiloxanes described in application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

 Mention may in particular be made, as oils of vegetable origin, of sweet almond oil, avocado oil, castor oil, olive oil,

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 jojoba, sunflower oil, wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, l safflower oil, coconut oil, corn oil, hazelnut oil, shea butter, palm oil, apricot kernel oil, calophyllum oil; as oil of animal origin, perhydrosqualene; as oils of mineral origin, paraffin oil and petrolatum oil.

 The polyisobutenes and poly (α-olefins) are chosen from those well known in the art.

 Examples of esters that may be mentioned in particular are fatty acid esters such as isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, Purcellin oil (stearyl octanoate), l 'isononyl or isostearyl isononanoate, isopropyl lanolate, and mixtures thereof.

 The anionic polymers generally used in the present invention are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids, and having a molecular weight by weight of between 500 and 5,000,000.

dans laquelle n est un nombre entier de 0 à 10, A désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement insaturé ou au groupement méthylène voisin lorsque n est supérieur à 1, par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R1 désigne un atome d'hydrogène, un groupement phényle ou benzyle, R2 désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, R3 désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement-CH2-COOH, phényle ou benzyle. The carboxylic groups are provided by monoacid or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:

in which n is an integer from 0 to 10, A denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as oxygen or sulfur, R1 denotes a hydrogen atom, a phenyl or benzyl group, R2 denotes a hydrogen atom, a lower alkyl or carboxyl group, R3 denotes a hydrogen atom, a lower alkyl group, a group- CH2-COOH, phenyl or benzyl.

 In formula (XII) above, a lower alkyl group preferably contains from 1 to 4 carbon atoms and denotes in particular the methyl and ethyl groups.

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The anionic polymers with carboxylic groups preferred according to the invention are:
A) homo- or copolymers of acrylic or methacrylic acid or their salts, and in particular the products sold under the names VERSICOL # E or K by the company ALLIED COLLOID, ULTRAHOLD by the company BASF Copolymers of acrylic acid and d 'acrylamide sold in the form of their sodium salt under the names RETEN # 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids.

 B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted on a polyalkylene glycol such as polyethylene glycol, and possibly crosslinked. Such polymers are described in particular in French patent 1 222 944 and German application No. 2 330 956, copolymers of this type comprising in their chain an acrylamide unit, optionally N-alkylated and / or hydroxyalkylated as described in particular in the applications of Luxembourg patents 75370 and 75371 or offered under the name QUADRAMER # by the company AMERICAN CYANAMID. Mention may also be made of the copolymers of acrylic acid and of C1-C4 alkyl methacrylate and of the copolymer of methacrylic acid and of ethyl acrylate sold under the name Luvimer # MAEX by the company BASF.

 C) copolymers derived from crotonic acid such as those comprising vinyl acetate or propionate units in their chain, and optionally other monomers such as the allyl or methallyl ester, vinyl ether or vinyl ester of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain, such as those containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or alternatively a vinyl, allyl or methallyl ester of an a or (3-cyclic) carboxylic acid. Such polymers are described inter alia in French patents numbers 1 222 944.1 580 545.2 265 782.2 265 781.1 564 110 and 2 439 798. Commercial products falling into this class are resins 28-29- 30.26-13-14 and 28-13-10 sold by the company NATIONAL STARCH.

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 D) Polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters; these polymers can be esterified. Such polymers are described in particular in US patents 2,047,398.2 723,248.2 102,113, GB patent 839,805, and in particular those sold under the names GANTREZ # AN or ES by the company ISP.

 Polymers also belonging to this class are the copolymers of maleic, citraconic, itaconic anhydrides and an allylic or methallylic ester optionally comprising an acrylamide, methacrylamide group, an α-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions are monoesterified or monoamidified. These polymers are for example described in French patents 2,350,384 and 2,357,241 of the applicant.

 E) Polyacrylamides containing carboxylate groups.

 The polymers comprising the sulfonic groups are polymers comprising vinylsulfonic, styrene-sulfonic, naphthalene-sulfonic or acrylamido-alkylsulfonic units.

 These polymers can in particular be chosen from: - the salts of polyvinylsulfonic acid having a molecular mass of between approximately 1,000 and 100,000 as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids, and their esters, as well as acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone; the salts of polystyrene-sulfonic acid, the sodium salts, having a molecular mass of approximately 500,000 and approximately 100,000 sold respectively under the names Flexan 500 and Flexan 130 by National Starch. These compounds are described in patent FR 2198719; - The salts of polyacrylamide-sulfonic acids such as those mentioned in US Pat. No. 4,128,631, and more particularly the polyacrylamidoethylpropane-sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel.

 According to the invention, the anionic polymers are preferably chosen from acrylic acid copolymers such as the acid terpolymer

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 acrylic / ethyl acrylate / N-tertiobutylacrylamide sold under the name ULTRAHOLD STRONG # by BASF, copolymers derived from crotonic acid such as vinyl acetate / vinyl tertiary butyl benzoate / crotonic acid and crotonic acid terpolymers / vinyl acetate / vinyl neododecanoate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, halides vinyl, phenylvinyl derivatives, acrylic acid and its esters such as the methylvinylether / maleic anhydride monoesterified copolymer sold under the name GANTREZ # ES 425 by the company ISP, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT # L by ROHM PHARMA, the copolymer of methacrylic acid and acrylic acid thyle sold under the name LUVIMER MAEX by the company BASF, the vinyl acetate / crotonic acid copolymer sold under the name LUVISET CA 66 by the company BASF and the vinyl acetate / crotonic acid / polyethylene glycol terpolymer under the name ARISTOFLEX # A BASF company.

 According to the invention, it is also possible to use anionic polymers in the form of latex or of pseudolatex, that is to say in the form of an aqueous dispersion of particles of insoluble polymers.

 Mention may in particular be made, as nonionic polymers which can be used according to the present invention: - vinylpyrrolidone homopolymers; - vinylpyrrolidone and vinyl acetate copolymers; - polyalkyloxazolines such as polyethyloxazolines offered by the company DOW CHEMICAL under the names PEOX # 50,000, PEOX 200,000 and PEOX # 500,000; - vinyl acetate homopolymers such as the product offered under the name of APPRETAN # EM by the company HOECHST or the product offered under the name of RHODOPAS # A 012 by the company RHONE POULENC;

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 - copolymers of vinyl acetate and acrylic ester such as the product offered under the name RHODOPAS AD 310 from RHONE POULENC; - copolymers of vinyl acetate and ethylene such as the product offered under the name of APPRETAN TV by the company HOECHST; - the copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate such as the product offered under the name of APPRETAN # MB EXTRA by the company HOECHST; - copolymers of polyethylene and maleic anhydride; homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates such as the product offered under the name MICROPEARL RQ 750 by the company MATSUMOTO or the product offered under the name LUHYDRAN A 848 S by the company BASF; - copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates, such as the products offered by the company ROHM & HAAS under the names PRIMAL # AC-261 K and EUDRAGIT # NE 30 D, by the company BASF under the names ACRONAL # 601, LUHYDRAN LR 8833 or 8845, by the company HOECHST under the names APPRETAN # N 9213 or N921 2; - copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; we can cite the products offered under the names NIPOL # LX 531 8 by the company NIPPON ZEON or those offered under the name CJ 0601 8 by the company ROHM &HAAS; - polyurethanes such as the products offered under the names ACRYSOL RM 1020 or ACRYSOL # RM 2020 by the company ROHM & HAAS, the products URAFLEX # XP 401 UZ, URAFLEX # XP 402 UZ by the company DSM RESINS; - copolymers of alkyl acetate and urethane such as the product 8538-33 by the company NATIONAL STARCH; - polyamides such as the product ESTAPOR LO 11 proposed by the company RHONE POULENC; - chemically modified or unmodified non-ionic guar gums.

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 Unmodified non-ionic guar gums are, for example, the products sold under the name VIDOGUM # GH 175 by the company UNIPECTINE and under the name JAGUAR C by the company MEYHALL.

 The modified nonionic guar gums which can be used according to the invention are preferably modified with C 1 -C 6 hydroxyalkyl groups. Mention may be made, by way of example, of the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

 These guar gums are well known in the art and can, for example, be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum so to obtain a guar gum modified with hydroxypropyl groups.

 Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names JAGUAR HP8, JAGUAR HP60 and JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL, or under the name GALACTASOL # 4H4FD2 by the company AQUALON.

 The alkyl groups of the nonionic polymers preferably contain from 1 to 6 carbon atoms.

 The reducing agents can be chosen from thioacids and their salts (thioglycolic or thiolactic acid, cysteine or cysteamine), sulphites of alkali or alkaline earth metals, reducing sugars such as glucose, vitamin C and its derivatives, derivatives of sulfinic acid, phosphines.

 The amounts of these various cosmetic active agents are those conventionally used in the fields under consideration, for example from 0.001 to 30% by weight relative to the total weight of the composition.

 The composition according to the invention can also comprise a solvent or a mixture of cosmetically acceptable solvents.

 By cosmetically acceptable is meant within the meaning of the invention physiologically acceptable solvents, non-toxic and capable of being applied to the skin or hair of human beings.

 As solvents which can be used according to the invention, mention may in particular be made of water, alcohols, preferably lower Ci-Ce alkanols and in particular ethanol, propanol and isopropanol, polyols such as

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 propyplene glycol, hexylene glycol, glycerin and pentanediol, polyol ethers, and mixtures thereof.

 The solvent (s) generally represent 0.1% to 99% of the total weight of the composition.

 The pH of the compositions according to the invention is preferably between 2 and 12, and even more preferably between 3 and 11.

 The composition of the invention may also contain conventional adjuvants such as perfumes, fillers, pH adjusters (acidic or basic), and preservatives.

 The amounts of these various adjuvants of the composition according to the invention are those conventionally used in cosmetics.

 Of course, a person skilled in the art will take care to choose any additional adjuvants and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not or substantially not altered by the envisaged addition.

 The present invention also relates to a process for treating keratin materials comprising the application to said keratin materials of a composition as defined above, and the irradiation of this composition to obtain a crosslinked deposit.

 In particular, the present invention relates to a process for treating keratin materials comprising the following steps: a) application to the keratin materials of a cosmetic composition according to the invention as defined above, and b) irradiation of said composition on keratin materials to crosslink the composition.

 The composition can be applied to wet or dry keratin materials, clean or not. Preferably, the keratin materials are dried after application of the composition and before irradiation.

 It is also possible to include in the process, before or after step b) of irradiation, a pause at ambient temperature, or under heat, or under red light.

 Finally, the process can comprise, prior to step b) of irradiation, a step of partial masking of keratin materials, and, after step b) of irradiation, a rinsing step, or when

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 keratin materials are hair, a shampooing or styling step.

 You can also make patterns on keratin materials. Preferably, the method comprises, in the case of the production of such patterns, a drying step prior to the step of partially masking said keratin materials and after the step of applying the composition. Thus, in practice, it is dried after application of the composition, then a part of the substrate is masked, for example with aluminum foil, and the whole area is irradiated. A rinse is then carried out. In the case of hair, this rinsing can be followed by a shampoo.

 This masking technique makes it possible in particular to obtain localized cosmetic effects by subsequent action of cosmetic active agents (for example dyes) having a selective affinity for the areas treated by the irradiation.

 The irradiation is preferably irradiation with radiation in the UVA or in the visible region, and even more preferably radiation in the UVA.

 By irradiation in the visible range is meant in the sense of the present invention, either an irradiation carried out with an appropriate device (laser or lamps), or the simple action of sunlight.

 When the keratin materials are hair, the method according to the invention can comprise, before or after step b) of irradiation, a step of shaping the hair, for example using tweezers, or curlers ...

 When the compound (s) comprising at least one photodimerizable group according to the invention is (are) also thermodimerizable (s), the various methods described above can be implemented by replacing the step of irradiation by a heating step between 40 and 200 C.

 The following example illustrates the invention without however limiting its scope.

The quantities are given, unless otherwise indicated, in mass percentages.

<Desc / Clms Page number 32>

EXAMPLE
An aqueous dispersion D is used of a polymer of the partially saponified polyvinylacetate type and carrying stilbazolium groups, adsorbed on polyvinylacetate particles.

 This dispersion contains a dry extract of 40%.

We make the following composition from this aqueous dispersion D:
Dispersion D 11.25 g
Dimethicone Copolyol 0. 5 g (marketed by Zshimmer Schwarz, under the name of SKINOTAN S10)
Water qs 100g
0.3 g of this composition is applied per g of hair.

 The lock is kneaded, combed and dried with a hair dryer.

 The lock was irradiated at 360 nm for 10 s for a total energy of 50 mJ / cm 2, or placed in daylight for 15 minutes.

 There is a deposit on the wick which is resistant to at least 5 successive shampoos.

Claims (32)

1. Cosmetic composition for the treatment of keratin materials comprising at least one cosmetic active agent, characterized in that it additionally comprises at least one compound comprising at least one photodimerizable group.  2. Cosmetic composition according to claim 1, characterized in that the photodimerizable group (s) is (are) chosen from monovalent radical radicals of formulas:

 in which: - Y and Z denote independently of one another a carbon or nitrogen atom, - A is a divalent linking group chosen from alkylene radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals , alkenylene radicals and their combinations, - B is a monovalent group chosen from alkyl radicals, cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenyl radicals and their combinations, - X is a divalent group chosen from alkylene radicals , cycloaromatic radicals, heterocyclic radicals, carbonyl radicals, alkenylene radicals and combinations thereof, and each of the groups mentioned possibly being substituted by one or more groups chosen from alkyl, hydroxy, amino, mono or dialkylamino groups, halogens, aryls, carboxy, alkoxy, alkoxycarbonyls, hydrogen carbonyls, sulfonato, amide, acyl s. <Desc / Clms Page number 34>  3. Cosmetic composition according to claim 2, characterized in that the photodimerizable group (s) is (are) chosen from monovalent radicals of the following compounds: - stilbene, - styrylpyridinium (stilbazolium) formula :

 where - R represents the hydrogen atom, an alkyl or hydroxyalkyl group, and - R 'represents the hydrogen atom or an alkyl group, - styrylazolium of formula:

 where A denotes a sulfur atom, an oxygen atom, or a group NR 'or C (R') 2, R and R 'being as defined above, - styrylpyrazine, - chalcone, - (thio) cinnamate and ( thio) cinnamamide, - maleimide, - (thio) coumarin, - thymine, - uracil, - butadiene - anthracene, - pyridone, - pyrrolizinone, - acridizinium salts, <Desc / Clms Page number 35>  - furanone, - phenylbenzoxazole, and - their derivatives.  4. Cosmetic composition according to any one of the preceding claims, characterized in that it is free of photoinitiator.  5. Cosmetic composition according to any one of the preceding claims, characterized in that the photodimerizable group (s) is (are) grafted (s) a support compound.  6. Cosmetic composition according to claim 5, characterized in that the support compound is chosen from poly (vinyl) polymers and polydiorganosiloxanes 7. Cosmetic composition according to claim 6, characterized in that the poly (vinyl) polymers are chosen from poly (vinyl acetate), preferably partially saponified.  8. Cosmetic composition according to any one of the preceding claims, characterized in that the compound (s) comprising at least one photodimerizable group is a polymer soluble or dispersed in the composition.  9. Cosmetic composition according to any one of the preceding claims, characterized in that the compound comprising at least one photodimerizable group is adsorbed on polymer particles, themselves dispersed in the composition.  10. Cosmetic composition according to claim 9, characterized in that the particles are particles of vinyl polymers.  11. Cosmetic composition according to claim 10, characterized in that the (poly) vinyl polymer is a poly (vinyl acetate).  12. Cosmetic composition according to any one of the preceding claims, characterized in that the compound comprising at least one photodimerizable group represents 0.01 to 25%, preferably 0.1 to 20%, and better still 1 to 15% by weight total of the composition.  13. Cosmetic composition according to any one of the preceding claims, characterized in that it also comprises an effective amount of at least one photosensitizer.  14. Cosmetic composition according to claim 12, characterized in that the photosensitizer (s) is (are) chosen from <Desc / Clms Page number 36>  thioxanthone, bengal rose, phloxine, eosin, erythrosine, fluorescein, acriflavin, thionin, riboflavin, proflavin, chlorophylls, hematoporphyrin, methylene blue and their mixtures.  15. Cosmetic composition according to claim 13 or 14, characterized in that the photosensitizer (s) represents (s) 0.00001% to 5% of the total weight of the composition.  16. Cosmetic composition according to any one of the preceding claims, characterized in that the cosmetic active ingredient (s) is (are) chosen from saccharides, oligosaccharides, polysaccharides which are hydrolyzed or not, modified or not; amino acids, oligopeptides, peptides, hydrolyzed proteins or not, modified or not, poly amino acids, enzymes; branched and unbranched fatty acids and alcohols; animal, vegetable or mineral waxes; ceramides and pseudoceramides; hydroxylated organic acids; UV filters; antioxidants and anti-free radical agents; chelators; anti-dandruff agents; seborrhea regulating agents; soothing agents; cationic surfactants; cationic, amphoteric polymers; organomodified or unorganized silicones; mineral, vegetable or animal oils; polyisobutenes and poly (α-olefins); esters; soluble or dispersed anionic polymers; soluble or dispersed nonionic polymers; reducing agents; coloring matters; foaming agents; film-forming agents; the particles ; and their mixtures.  17. Cosmetic composition according to claim 16, characterized in that the (or) active (s) cosmetic (s) represents (s) 0.001 to 30% of the total weight of the composition.  18. Cosmetic composition according to any one of the preceding claims, characterized in that it also comprises a solvent or a mixture of cosmetically acceptable solvents.  19. Cosmetic composition according to claim 18, characterized in that the solvent is chosen from water, alcohols, polyols, polyol ethers and their mixtures.  20. Cosmetic composition according to claim 19, characterized in that the alcohols are lower Ci-Ce alkanols, and preferably chosen from ethanol, propanol and isopropanol. <Desc / Clms Page number 37>  21. Cosmetic composition according to claim 19, characterized in that the polyols are chosen from propylene glycol, hexylene glycol, glycerin, and pentanediol.  22. Cosmetic composition according to one of claims 18 to 21, characterized in that the solvent (s) represent (s) 0.1% to 99% of the total weight of the composition.  23. Cosmetic composition, characterized in that it has a pH of between 2 and 12, and preferably between 3 and 11.  24. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises at least one adjuvant chosen from perfumes, fillers, pH adjusters, and preservatives.  25. A method of treating keratin materials comprising the following steps: a) application to the keratin materials of a composition as defined according to any one of claims 1 to 24, and b) irradiation of said composition on the keratin materials for crosslink the composition.  26. The method of claim 25, characterized in that it comprises, before the irradiation step and after the application step, drying of the keratin materials.  27. The method of claim 25 or 26, characterized in that it comprises, before or after step (b) of irradiation, a pause at room temperature, or under heat, or under red light.  28. Method according to one of claims 25 to 27, characterized in that it comprises, prior to step (b) of irradiation, a step of partial masking of keratin materials and, after step (b ) irradiation, a rinsing step, or when the keratin materials are hair, a shampooing or styling step.  29. The method of claim 28, characterized in that it comprises, prior to the step of partially masking keratin materials and after the step of applying the composition, a step of drying the keratin materials.  30. Method according to any one of claims 25 to 29, characterized in that the irradiation is an irradiation with a radiation <Desc / Clms Page number 38>  in the UVA or in the visible range, and preferably radiation in the UVA.  31. Method according to any one of claims 25 to 30, characterized in that, when the keratin materials are hair, it further comprises, before or after step (b) of irradiation, a step of hair shaping.  32. Method according to any one of claims 25 to 30, characterized in that the compound (s) comprising at least one photodimerizable group is (are) also thermodimerizable (s), and in that the step irradiation is replaced by a heating step between 40 and 200 C.